Silver halide color light-sensitive material

ABSTRACT

A silver halide color light-sensitive material having excellent properties for a sensitization treatment is described, containing a polymer coupler having an average molecular weight higher than 30,000 and having a polymeric unit derived from a monomeric magenta coupler represented by formula (I): ##STR1## wherein R 1  is hydrogen, chlorine, or a lower alkyl group having 1 to 4 carbon atoms; A is a phenylene group, a --CONH-- group, or a --COO-- group; B is an unsubstituted or substituted alkylene group, an unsubstituted or substituted aralkylene group, or an unsubstituted or substituted phenylene group; Y is --O--, --NH--, --S--, --SO--, --SO 2  --, --CONH--, --COO--, --NHCO--, or --NHCONH--; Q is a residue of a megenta color-forming coupler which forms a dye through coupling with the oxidation product of an aromatic primary amine developer; and m is 1 when n is 1, and m is 0 or 1 when n is 0.

This is a continuation-in-part application of Ser. No. 632,736, filedJuly 20, 1984, now abandoned.

FIELD OF THE INVENTION

The present invention relates to a silver halide color light-sensitivematerial, and more particularly to a reversal color light-sensitivematerial which has excellent properties for a sensitization treatment.

BACKGROUND OF THE INVENTION

At present, the silver halide color light-sensitive materials typicallyresort to subtractive color reproduction using three primary colors.According to this process, the color image is formed by the combinationof three dyes derived from a yellow color-forming coupler, a magentacolor-forming coupler, and a cyan color-forming coupler.

Of the magenta color-forming couplers, nitrogen-containing heterocycliccompounds such as 5-pyrazolones are in general use. Such couplers havesome disadvantages. Particularly, they are liable to restraindevelopment. An emulsion layer containing such a coupler tends to beless sensitive and to yield a softer gradation than an emulsion layer ofthe same sensitivity and gradation containing a phenol-type coupler,naphthol-type coupler, and acetanilide-type coupler. Thus it isnecessary to increase the sensitivity and gradation of the emulsionlayer containing a magenta coupler and to control the amount of theemulsion to be applied in order to establish proper color balance. At aresult, the magenta image tends to be inferior in graininess andsharpness to the other color images.

Since the coarse graininess of the magenta image stands out, a magentaimage of poor graininess is fatal to the light-sensitive material. Thetendency toward low sensitivity is a disadvantage in sensitizationtreatment which is carried out in reversal color development as noted inExample 1 in order to raise the sensitivity by extending the usualdevelopment time of the first development or the black-and-whitedevelopment. In other words, the tendency toward low sensitivitydestroys the color balance of yellow color-forming, magentacolor-forming and cyan color-forming in the sensitization treatment.Thus, reversal color light-sensitive materials containing suchabove-mentioned magenta couplers have poor properties for thesensitization treatment. This is a fatal drawback for reversal colorlight-sensitive materials, which must often undergo a sensitizationtreatment.

SUMMARY OF THE INVENTION

One object of this invention is to provide a color light-sensitivematerial having high sensitivity.

Another object of this invention is to provide a reversal colorlight-sensitive material which has excellent properties for asensitization treatment.

Still another object of this invention is to provide a colorlight-sensitive material which is superior in graininess.

The objects of this invention are achieved with a silver halide colorlight-sensitive material which contains a polymer coupler having anumber average molecular weight higher than 30,000 and having apolymeric unit derived from a monomeric magenta coupler represented byformula (I): ##STR2## wherein R₁ is hydrogen, chlorine, or a lower alkylgroup having 1 to 4 carbon atoms; A is a phenylene group, a --CONH--group, or a --COO-- group; B is an unsubstituted or substituted alkylenegroup which may be either linear or branched, an unsubstituted orsubstituted aralkylene group, or an unsubstituted or substitutedphenylene group; Y is --OH--, --NH--, --S--, --SO--, --SO₂ --, --CONH--,--COO--, --NHCO--, or --NHCONH--; Q is a residue of a magentacolor-forming coupler which forms a dye through coupling with theoxidation product of an aromatic primary amine developer; and m is 1when n is 1, and m is 0 or 1 when n is 0.

DETAILED DESCRIPTION OF THE INVENTION

The following is a more detailed description including preferredembodiments of B and Q according to formula (I).

B is an unsubstituted or substitued alkylene group having 1 to 10 carbonatoms which may be either linear of branched, an unsubsituted orsubstituted aralkylene group, or an unsubstituted or substitutedphenylene group. The alkylene group includes, for example, methylene,methylmethylene, dimethylmethylene, dimethylene, trimethylene,tetramethylene, pentamethylene, hexamethylene, and decylmethylene. Thearalkylene group includes, for example, benzilidene. The phenylene groupincludes, for example, p-phenylene, m-phenylene, and methylphenylene.

The substituent of the alkylene, aralkylene, or phenylene grouprepresented by B can include an aryl group (e.g., a phenyl group), anitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxygroup (e.g., a methoxy group), an aryloxy group (e.g., a phenoxy group),an acyloxy group (e.g., an acetoxy group) an acylamino group (e.g., anacetylamino group), a sulfonamido group (e.g., a methanesulfonamidogroup), a sulfamoyl group (e.g., a methylsulfamoyl group), a halogenatom (e.g., a fluorine atom, a chlorine atom, and a bormine atom), acarboxyl group, a carbamoyl group (e.g., a methylcarbamoyl group), analkoxycarbonyl group (e.g., a methoxycarbonyl group), and a sulfonylgroup (e.g., a methylsulfonyl group). Where there are two or moresubstituents, they may be the same or different.

The residue of the magenta color-forming coupler represented by Q ispreferably of pyrazolone type, pyrazolotriazole type, or imidazopyrazoletype. Examples of useful residues are represented as follows. ##STR3##

The pyrazolo[1,5-b][1,2,4]triazole residue represented by formula (7) isexcellent because of less side-absorption of yellow color of theresulting dye and high light fastness.

In the foregoing residue formulae, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ eachrepresents a hydrogen atom, a hydroxyl group, an unsubstituted orsubstituted alkyl group (preferably having from 1 to 20 carbon atoms,such as a methyl group, a propyl group, a t-butyl groups, atrifluoromethyl group, and a tridecyl group), an aryl group (preferablyhaving from 6 to 20 carbon atoms, such as a phenyl group, a4-t-butylphenyl group, a 2,4-di-t-aminophenyl group, and a4-methoxyphenyl group), a heterocyclic group (e.g., a 2-furyl group, a2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group),an alkylamino group (preferably having from 1 to 20 carbon atoms, suchas a methylamino group, a diethylamino group, and a t-butylamino group),an acylamino group (preferably having from 2 to 20 carbon atoms, such asan acetylamino group, a propylamido, and a benzamido group), an anilinogroup (e.g., a phenylamino group and a 2-chloroanilino group), analkoxycarbonyl group (preferably having from 2 to 20 carbon atoms, suchas a methoxycarbonyl group, a butoxycarbonyl group, and a2-ethylhexyloxycarbonyl group), an alkylcarbonyl group (preferablyhaving from 2 to 20 carbon atoms, such as an acetyl group, abutylcarbonyl group, and a cyclohexylcarbonyl group), an arylcarbonylgroup (preferably having from 7 to 20 carbon atoms, such as a benzoylgroup and a 4-t-butylbenzoyl group), an alkylthio group (preferablyhaving from 1 to 20 carbon atoms, such as a methylthio group, anoctylthio group, and a 2-phenoxyethylthio group), an arylthio group(preferably having from 6 to 20 carbon atoms, such as a phenylthio groupand a 2-butoxy-5-t-octylphenylthio group), a carbamoyl group (preferablyhaving from 1 to 20 carbon atoms, such as an N-ethylcarbamoyl group, anN,N-dibutylcarbamoyl group, and an N-methyl-N-butylcarbamoyl group), asulfamoyl group (preferably having up to 20 carbon atoms, such as anN-ethylsulfamoyl group, an N,N-diethylsulfamoyl group, and anN,N-dipropylsulfamoyl group), and a sulfonamido group (preferably havingfrom 1 to 20 carbon atoms, such as a methanesulfonamido group, abenzenesulfonamido group, and a p-toluenesulfonamido group).

X denotes a hydrogen atom or an elimination group bonded to the couplingposition through an oxygen atom, a nitrogen atom, or a sulfur atom. WhenX is bonded to the coupling position through an oxygen atom, a nitrogenatom, or a sulfur atom, such an atom is bonded to an alkyl group, anaryl group, an alkylsulfonyl group, an arylsulfonyl group, analkylcarbonyl group, an arylcarbonyl group, or a heterocyclicgroup.(Said alkyl group, aryl group, and heterocyclic group may have asubstituent. Examples of the substituent include, for example, an alkylgroup (e.g., a methyl group and an ethyl group), an alkoxy group (e.g.,a methoxy group and an ethoxy group), an aryloxy group (e.g., aphenyloxy group), an alkoxycarbonyl group (e.g., a methoxycarbonylgroup), an acylamino group (e.g., an acetylamino group), a carbamoylgroup, an alkylcarbamoyl group (e.g., a methylcarbamoyl group and anethylcarbamoyl group), a dialkylcarbamoyl group (e.g., adimethylcarbamoyl group), an arylcarbamoyl group (e.g., aphenylcarbamoyl group), an alkylsulfonyl group (e.g., a methylsulfonylgroup), an arylsulfonyl group (e.g., a phenylsulfonyl group), analkylsulfonamido group (e.g., a methanesulfonamido group), anarylsulfonamido group (e.g., a phenylsulfonamido group), a sulfamoylgroup, an alkylsulfamoyl group (e.g., an ethylsulfamoyl group), adialkylsulfamoyl group (e.g., a dimethylsulfamoyl group), an alkylthiogroup (e.g., a methylthio group), an arylthio group (e.g., a phenylthiogroup), a cyano group, a nitro group, and a halogen atom (e.g., afluorine atom, a chlorine atom, and a bromine atom). Where there are twoor more substituents, they may be the same or different. Preferredsubstituents are a halogen atom, an alkyl group, an alkoxy group, analkoxycarbonyl group, and a cyano group.) The group bonded to a nitrogenatom includes any group that contains the nitrogen atom and forms afive- or six-membered ring and that can be an elimination group (e.g.,an imidazolyl group, a pyrazolyl group, a triazolyl group, and atetrazolyl group).

Examples of the monomeric magenta coupler (from which the polymeric unitis derived for forming the polymer coupler) represented by formula (I)are set forth below. ##STR4##

With respect to the 1-phenyl-2-pyrazolin-5-one type magenta coupler,those in which the 1-phenyl group thereof has chlorine atoms at the 2-,4- and 6-positions thereof give a most excellent graininess, andtherefore, they are more preferable than those in which the 1-phenylgroup thereof has chlorine atoms at the 2- and 5-positions thereof.

The polymer coupler preferably has a number average molecular weighthigher than 45,000 and more preferably higher than 80,000, but lowerthan 1,000,000 and more preferably lower than 500,000.

The polymer coupler is used in an amount of from 2×10⁻³ mol to 5×10⁻¹mol, and preferably more than 1×10⁻² mol, as a color-forming unit, permol of silver.

The polymer coupler of the present invention may be a homopolymer of themonomeric coupler represented by formula (I) or a copolymer betweenmonomer coupler (I) and an ethylenically unsaturated monomeric couplerwhich does not couple with an oxidation product of an aromatic primaryamine developer (and therefore forms no color). In any of thesepolymers, two or more monomeric coupler included within formula (I) maybe used as monomeric coupler (I).

Examples of the ethylenically unsaturated monomer which is incapable ofcoupling with the oxidation product of an aromatic primary aminedeveloper include esters or amides drived from acrylic acid,α-chloroacrylic acid, α-alkyl acrylic acids (e.g. methacrylic acid,etc.) and the like (e.g., ethyl acrylate, n-propyl acrylate, n-butylacrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate,cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butylmethacrylate, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamideand n-butylmethacrylamide), vinyl esters (e.g., vinyl acetate and vinylpropionate), styrene and the like. In particular, acrylates andmetahcrylates are preferably used.

The non-color forming ethyleneically unsaturated monomer used here maybe used together with two kinds or more. For example, the combinationsof ethyl acrylate and n-butyl acrylate, n-butyl acrylate and styrene,and methyl methacrylate and diacetoneacrylamide may be used.

The ethylenically unsaturated monomer which is used to copolymerize withthe monomeric coupler represented by the above-described general formula(I) can be selected so that the copolymer to be formed possesses goodphysical properties and/or chemical properties, for example, solubility,compatibility with a binder such as gelatin in a photographic colloidcomposition, flexibility, heat stability, etc., as well known in thefield of polymer color couplers.

The polymer coupler used in this invention is oleophilic and, inparticular, preferably used in a latex form.

For the process of emulsion dispersion of an oleophilic polymer couplerin a latex form in a gelatin aqueous solution, the process described inU.S. Pat. No. 3,451,820 can be employed.

General polymerization processes of an oleopholic polymer coupler aredescribed below.

The free redical polymerization of the ethylenically unsaturated monomeris initiated with the addition to the monomer molecule of a free radicalwhich is formed by thermal decomposition of a chemical polymerizationinitiator or a physical action, e.g., irradiation of ultraviolet rays orother high energy radiations, high frequencies, etc.

Examples of the main chemical polymerization initiators include azobistype polymerization initiators (e.g., dimethyl 2,2'-azobisisobutyrate,diethyl 2,2'-azobisisobutyrate, 2,2'-azobisisobutyronitrile,2,2'-azobis-(2,4-dimethylvalenonitrile), etc.), benzoyl peroxide,chlorobenzoyl peroxide and other compounds.

Organic solvents which can be used in polymerization of the oleophilicpolymer couplers are preferably those which can usually be admixed withmonomers to be used without limitation, are good solvent for theoleophilic polymer coupler formed, do not react with initiators to beused and do not interrupt usual actions in free radical additionpolymerization.

Specific useful examples of the organic solvent include aromatichydrocarbons (e.g., benzene, toluene, etc.), hydrocarbons (e.g.,n-hexane, etc.), alchohols (e.g., methanol, ethanol, n-propanol,isopropanol, tertbutanol, etc.), ketones (e.g., acetone, methyl ethylketone, etc.), cyclic ethers (e.g., tetrahydrofuran, dioxane, etc.),esters (e.g., ethyl acetate, etc.), chlorinated hydrocarbons (e.g.,methylene chloride, chloroform, etc.), amides (e.g., dimethylformamide,dimethylacetamide, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.),nitriles (e.g., acetonitrile, etc.) and combinations thereof.

When the oleophilic polymer coupler is dispersed in a latex form in agelatin aqueous solution, the organic solvent used for dissolving theoleophilic polymer coupler is removed from the mixture before coatingthe dispersed solution or at vaporization during drying of the coateddispersed solution, although the latter is rather unpreferable.

With respect to removing the solvent, a method in which the solvent isremoved by washing a gelatin noodle with water is applied when thesolvent is water-soluble to some extent, or a spray drying method, avacuum purging method or a steam purging method can be employed forremoving the solvent.

Examples of removable organic solvents include esters (such as loweralkyl esters), lower alkyl ethers, ketones, halogenated hydrocarbons(e.g., methylene chloride, trichloroethylene or hydrocarbon fluoride),alcohols (e.g., alcohols between n-butyl alcohol and octyl alcohol), andcombinations thereof.

As the dispersing agent to disperse the oleophilic polymer coupler, anytype agents may be used, but an ionic surfactant, in particular, anionictype surfactant, is suitable. The amphoteric type surfactant such asN-alkylaminopropionic acid salts and N-alkyliminodipropionic acid saltsmay be also used.

In order to control the color hue of dyes formed from the oleophilicpolymer coupler and the oxidation product of an aromatic primary aminedeveloper and to improve the bending property of the coated emulsion, apermanent solvent, i.e., a water non-miscible organic solvent having ahigh boiling point (200° C. or more), may be added.

Also, in order to make the final emulsion layer as thin as possible andto maintain a high sharpness, the concentration of the permanent solventis preferably low.

It is desirable that the ratio of the color forming portioncorresponding to the general formula (I) in the oleophilic polymercoupler is usually from 5 to 80% by weight. Particularly, a ratio from20 to 70% by weight is preferred in view of color reproducibility, colorforming property and stability. In this case, an equivalent molecularweight, that is, a gram number of the polymer containing 1 mol of themonomeric coupler, is preferably from about 250 to 4,000, but it is notlimited thereto.

In this invention, the average molecular weight was measured by the gelpermeation chromatography (GPC) under the following conditions.

Column: TSK gel (a trade mark for cross-linked polystyrene, made by ToyoSoda Manufacturing Co., Ltd.);

G2000H8: 1 unit; (Molecular weight of exclusion limit: 10,000); (Columndimensions: 7.51 mm(D)×600 mm(L))

G4000H8: 1 unit; (Molecular weight of exclusion unit: 400,000); (Columndimensions: 7.51 mm(D)×600 mm(L))

Solvent: THF (tetrahydrofuran)

Flow rate: 1 ml/min

Column temperature: 40° C.

Detect: UV-8 Model II (made by Toyo Soda Manufacturing Co., Ltd.)

A calibration curve was prepared by using TSK standard polystyrene.

Preparation Example (1) for polymer coupler (I)

Copolymer coupler composed of1-(2,4,6-trichlorophenyl)-3-methacrylamido-2-pyrazolin-5-one (C-1) andbutyl acrylate:

A mixture of 50 g of monomeric coupler (C-1), 50 g of butyl acrylate,and 300 g of dimethylacetamide was heated at 60° C. with stirring in anitrogen stream. Then 10 ml of dimethylacetamide containing 0.5 g ofdimethyl azobisisobutyrate was added to initiate polymerization. Afterreaction for 5 hours, the reaction liquid was cooled and poured into 3liters of water. The solid which had separated out was filtered off,washed thoroughly with water, and dried with heating under reducedpressure. Thus there was obtained 96.2 g of polymer coupler (I).

It was indicated by chlorine analysis that this copolymer contains 52.0%of monomeric coupler (C-1). GPC gave a number average molecular weightof 105,000.

Preparation Example (2) for polymer coupler (II)

Copolymer coupler composed of1-(2,4,6-trichlorophenyl)-3-methacrylamido-2-pyrazolin-5-one (C-1) andbutyl acrylate:

A mixture of 50 g of monomeric coupler (C-1), 50 g of butyl acrylate,and 300 g of dimethylacetamide was heated at 70° C. with stirring in anitrogen stream. Then 10 ml of dimethylacetamide containing 0.5 g ofdimethyl azobisisobutyrate was added to initiate polymerization. Afterreaction for 5 hours, the reaction liquid was cooled and poured into 3liters of water. The solid which had separated out was filtered off,washed thoroughly with water, and dried with heating under reducedpressure. Thus there was obtained 97.1 g of polymer coupler (II).

It was indicated by chlorine analysis that this copolymer contains 51.6%of monomeric coupler (C-1). GPC gave a number average molecular weightof 48,000.

Preparation Examples (3) to (10)

Polymer couplers (III) to (X) were prepared in an analogous manner tothat used in Preparation Example (1); the characteristics thereof areindicated in Table 1 below:

                                      TABLE 1                                     __________________________________________________________________________                         Non-color                                                                              Monomeric coupler                               Preparation                                                                         Polymer                                                                            Monomeric coupler                                                                       forming monomer                                                                        unit in polymer                                                                         Number average                        Example                                                                             coupler                                                                            Type Amount                                                                             Type                                                                              Amount                                                                             (wt %)    molecular weight                      __________________________________________________________________________    3     III  C-1  30 g EA  30 g 51.2      96,000                                4     IV   C-1  30 g 2-EHA                                                                             30 g 52.5      108,000                               5     V    C-2  30 g BA  40 g 44.7      98,000                                6     VI   C-4  30 g BA  30 g 51.8      107,000                               7     VII  C-7  30 g EA  40 g 43.9      96,000                                8     VIII C-7  30 g BA  30 g 51.6      98,000                                9     IX   C-9  30 g BA  30 g 48.7      96,000                                                     MAA  5 g                                                 10    X    C-10 30 g BA  30 g 50.9      92,000                                __________________________________________________________________________     EA: Ethyl acrylate                                                            BA: Butyl acrylate                                                            2EHA: 2Ethylhexyl acrylate                                                    MAA: Methacrylic acid                                                    

Comparative Example (1)

Copolymer coupler composed of1-(2,4,6-trichlorophenyl)-3-methacrylamido-2-pyrazolin-5-one (C-1) andbutyl acrylate. (Polymer coupler (A) as a comparative example):

A mixture of 50 g of monomeric coupler (C-1), 50 g of butyl acrylate,and 500 g of dimethylacetamide was heated at 80° C. with stirring in anitrogen stream. Then 10 ml of dimethylacetamide containing 1.0 g ofdimethyl azobisisobutyrate was added to initiate polymerization. Afterreaction for 5 hours, the reaction liquid was cooled and poured into 3liters of water. The solid which had separated out was filtered off,washed thoroughly with water, and dried with heating under reducedpressure. Thus there was obtained 97.5 g of polymer coupler (A) as acomparative example.

It was indicated by chlorine analysis that this copolymer contains 50.8%of monomeric coupler (C-1). GPC gave a number average molecular weightof 15,000.

The effect of this invention is to overcome the disadvantage of theconventional magenta coupler by using certain magenta couplers havinghigh molecular weight. In the case of a conventional magenta coupler,the nucleus is a nitrogen-containing heterocyclic ring, and thisheterocyclic ring tends to be adsorbed to the surface of silver halide.This adsorption delays the development of silver halide, and hencelowers the sensitivity. The polymer coupler according to the presentinvention having a high molecular weight is inhibited to be adsorbed tosilver halide, and thus the silver halide exhibits its inherentsensitivity. The polymer coupler should have a number average molecularweight higher than 30,000. A conventional polymer coupler having anumber average molecular weight of about 10,000 still has a tendency tolower the sensitivity of emulsion.

The photographic light-sensitive material produced according to thisinvention may contain a conventional magenta coupler of low molecularweight in addition to the magenta polymer coupler. Such magenta couplersinclude 5-pyrazolone coupler, pyrazolobenzimidazole coupler,cyanoacetylcoumarone coupler, and open chain acylacetonitrile coupler.

The photographic light-sensitive material produced according to thisinvention may contain a yellow coupler and a cyan coupler in addition tothe magenta coupler. The yellow coupler includes acylacetamide coupler(e.g., benzoylacetanilide and pivaloylacetanilide). The cyan couplerincludes naphthol coupler and phenol coupler. These couplers shouldpreferably be of a nondiffusible type which has a hydrophobic group,also preferred to as a ballast group, in the molecule The coupler may be4-equivalent or 2-equivalent with respect to the silver ion. Inaddition, the coupler may be one which has a color correction effect orone which releases the development inhibitor as development proceeds(i.e., a so-called DIR coupler).

Furthermore, the photographic light-sensitive material of this inventionmay contain, in addition to a DIR coupler, a non-color developing DIRcoupling compound which forms a colorless coupling reaction product andreleases a development inhibitor.

The photographic emulsion used in this invention may be produced by theprocesses described in Chimie et Physique Photographique, by P.Glafkides (published by Paul Montel, 1967), Photographic EmulsionChemistry, by G. F. Duffin (published by The Focal Press, 1966), andMaking and Coating Photographic Emulsions, by V. L. Zelikman et al.(published by The Focal Press, 1964). In other words, it may be producedby acidic process, neutral process, or ammoniacal process. The reactionof soluble silver salt and soluble halogen salt may be accomplished by asingle jet method, a double jet method, or a combination thereof.According to another process (so-called reverse mixing), the grains areformed in the presence of excess silver ions. It is also possible toemploy a so-called controlled double jet method which is one type of thedouble jet method. According to this method, the pAg in the liquid phasein which silver halide is formed is kept constant. This method providesa silver halide emulsion in which the crystals have the regular shapeand uniform grain size.

It is also permissible to mix two or more kinds of silver halideemulsions which have been prepared individually.

The formation or physical ripening of silver halide grains may beaccomplished in the presence of a cadmium salt, a zinc salt, a leadsalt, a thallium salt, an iridium salt or a complex thereof, a rhodiumsalt or a complex thereof, or an iron salt or a complex thereof.

The silver halide grains in the photographic emulsion may be regularcrystals such as cubic and octahedral, or irregular crystals such asspherical and tabular (having a length/thickness ratio greater than 5,or even greater than 8), or crystals of complex forms. A mixture ofgrains of various crystal forms is also acceptable.

The silver halide grains may be composed of the internal layer andexternal layer which are different from each other, or may be composedof a uniform phase. They may be such that the latent image is formedmainly on the surface thereof, or may be such that the latent image isformed mainly inside the grain.

The light-sensitive material of this invention may contain a colorantifoggant such as a hydroquinone derivative, an aminophenolderivative, a gallic acid derivative, and an ascorbic acid derivative.

The light-sensitive material of this invention may contain in thehydrophilic colloid layer a water-soluble dye as a filter dye, or forthe prevention of irradiation and other purposes. Examples of such a dyeinclude an oxonol dye, a hemioxonol dye, a stryryl dye, a merocyaninedye, a cyanine dye, and an azo dye. Useful among them are an oxonol dye,a hemioxonol dye, and a merocyanine dye.

The photographic emulsion of this invention may be incorporated withvarious compounds in order to prevent the photographic fog that mightoccur in the production or preservation of the light-sensitive materialor in the photographic processing, or in order to stabilize thephotographic performance. Examples of these compounds include knownantifoggants and stabilizers, for example, azoles such asbenzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, andbenzimidazoles (particularly nitro- or halogen-substituted ones);heterocyclic mercapto compounds such as mercaptothiazoles,mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles,mercaptotetrazoles (particularly 2-phenyl-5-mercaptotetrazole), andmercaptopyrimidines; those among the above-mentioned heterocyclicmercapto compounds which have a water-soluble group such as a carboxylgroup and a sulfone group; thioketo compounds such as oxazolinethione;azaindenes (particularly 4-hydroxy-substituted(1,3,3a,7)tetraazaindenes); benzenethiosulfonic acids; andbenzenesulfinic acid.

The photographic emulsion layer of the light-sensitive material of thisinvention may contain, for the purpose of sensitivity increase, contrastincrease, and development acceleration, polyalkylene oxides orderivatives thereof such as ethers, esters, and amines, thioethercompounds, thiomorpholines, quaternary ammonium salts, urethanederivatives, urea derivatives, imidazole derivatives, and3-pyrazolidones.

EXAMPLE 1

Sample A of multilayered film was prepared by coating emulsion layersand auxiliary layers, in the order mentioned below, on a triacetylcellulose support. The 1st layer: Slow-speed red sensitive emulsionlayer

An emulsion was prepared by dissolving 100 g of a cyan coupler(2-(heptafluorobutylamide)-5-[2'-(2",4"-di-t-aminophenoxy)butylamide]-phenol)in 100 cc of tricresyl phosphate and 100 cc of ethyl acetate, and mixingwith high speed agitation the resulting solution with 1 kg of 10%aqueous solution of gelatin. 500 g of the emulsion was mixed with 1 kgof slow-speed red sensitive silver iodobromide emulsion (containing 70 gof silver and 60 g of gelatin and 6 mol % of iodine; having a grain sizedistribution such that 81% of the total number of silver halide grainsfalls under ±40% of the average grain size). The resulting emulsion wasapplied to the support so that the dry layer thereof was 2 μm thick(silver quantity: 0.5 g/m²).

The 2nd layer: Medium-speed red sensitive layer

An emulsion was prepared by dissolving 100 g of a cyan coupler(2-(heptafluorobutylamide)-5-[2'-(2",4"-di-t-aminophenoxy)butylamide]-phenol)in 100 cc of tricresyl phosphate and 100 cc of ethyl acetate, and mixingwith high speed agitation the resulting solution with 1 kg of 10%aqueous solution of gelatin. 1000 g of the emulsion was mixed with 1 kgof medium-speed red sensitive silver iodobromide emulsion (containing 70g of silver and 60 g of gelatin and 6 mol % of iodine; having a grainsize distribution of 76% measured as mentioned above for the 1st layer).The resulting emulsion was applied so that the dry layer thereof was 1μm thick (silver quantity: 0.4 g/m²)

The 3rd layer: High-speed red sensitive layer

An emulsion was prepared by dissolving 100 g of a cyan coupler(2-(heptafluorobutylamide)-5-[2'-(2",4"-di-t-aminophenoxy)butylamide]-phenol)in 100 cc of tricresyl phosphate and 100 cc of ethyl acetate, and mixingwith high speed agitation the resulting solution with 1 kg of 10%aqueous solution of gelatin. 1000 g of the emulsion was mixed with 1 kgof high-speed red sensitive silver iodobromide emulsion (containing 70 gof silver and 60 g of gelatin and 6 mol % of iodine; having a grain sizedistribution of 78% measured as mentioned above). The resulting emulsionwas applied so that the dry layer thereof was 1 μm thick (silverquantity: 0.4 g/m²).

The 4th layer: Interlayer

An emulsion was prepared by dissolving 2,5-di-t-octylhydroquinone in 100cc of dibutyl phthalate and 100 cc of ethyl acetate, and mixing withhigh speed agitation the resulting solution with 1 kg of 10% aqueoussolution of gelatin. 1 kg of the emulsion was mixed with 1 kg of 10%aqueous solution of gelatin. The resulting emulsion was applied so thatthe dry layer thereof was 1 μm thick.

The 5th layer: Slow-speed green sensitive emulsion layer

An emulsion was prepared in the same way as for the 1st layer, exceptthat the cyan coupler was replaced by a magenta coupler(1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone).500 g of the emulsion was mixed with 1 kg of slow-speed green sensitivesilver iodobromide emulsion (containing 70 g of silver and 60 g ofgelatin and 5.2 mol % of iodine; having a grain size distribution of 81%measured as mentioned above). The resulting emulsion was applied so thatthe dry layer thereof was 2.0 μm thick (silver quantity: 0.7 g/m²)

The 6th layer: Medium-speed green sensitive emulsion layer

An emulsion was prepared in the same way as for the 1st layer, exceptthat the cyan coupler was replaced by a magenta coupler(1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)behzamide]-5-pyrazolone).1000 g of the emulsion was mixed with 1 kg of high-speed green sensitivesilver iodobromide emulsion (containing 70 g of silver and 60 g ofgelatin and 5.2 mol % of iodine; having a grain size distribution of 75%measured as mentioned above). The resulting emulsion was applied so thatthe dry layer thereof was 1 μm thick (silver quantity: 0.35 g/m²).

The 7th layer: High-speed green sensitive emulsion layer

An emulsion was prepared in the same way as for the 1st layer, exceptthat the cyan coupler was replaced by a magenta coupler(1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone).1000 g of the emulsion was mixed with 1 kg of high-speed green sensitivesilver iodobromide emulsion (containing 70 g of silver and 60 g ofgelatin and 5.2 mol % of iodine; having a grain size distribution of 75%measured as mentioned above). The resulting emulsion was applied so thatthe dry layer thereof was 1 μm thick (silver quantity: 0.35 g/m²).

The 8th layer: Interlayer

1 kg of the emulsion as used for the 4th layer was mixed with 1 kg of10% aqueous solution of gelatin. The emulsion was applied so that thedry layer thereof was 1 μm thick.

The 9th layer: Yellow filter layer

An emulsion containing yellow colloidal silver was applied so that thedry layer thereof was 1 μm thick.

The 10th layer: Slow-speed blue sensitive emulsion layer

An emulsion was prepared in the same way as for the 1st layer, exceptthat the cyan coupler was replaced by a yellow coupler(α-(pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonyl-acetanilide).1000 g of the emulsion was mixed with 1 kg of slow-speed blue sensitivesilver iodobromide emulsion (containing 70 g of silver and 60 g ofgelatin and 5.5 mol % of iodine; having a grain size distribution of 77%measured as mentioned above). The resulting emulsion was applied so thatthe dry layer thereof was 2.0 μm thick (silver quantity: 0.6 g/m²).

The 11th layer: Medium-speed blue sensitive emulsion layer

An emulsion was prepared in the same way as for the lst layer, exceptthat the cyan coupler was replaced by a yellow coupler(α-(pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonyl-acetanilide).1000 g of the emulsion was mixed with 1 kg of high-speed blue sensitivesilver iodobromide emulsion (containing 70 g of silver and 60 g ofgelatin and 5.5 mol % of iodine; having a grain size distribution of 72%measured as mentioned above). The resulting emulsion was applied so thatthe dry layer thereof was 1.0 μm thick (silver quantity: 0.5 g/m²).

The 12th layer: High-speed blue sensitive emulsion layer

An emulsion was prepared in the same way as for the 1st layer, exceptthat the cyan coupler was replaced by a yellow coupler(α-(pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonyl-acetanilide). 1000 g of theemulsion was mixed with 1 kg of high-speed blue sensitive silveriodobromide emulsion (containing 70 g of silver and 60 g of gelatin and5.5 mol % of iodine; having a grain size distribution of 72% measured asmentioned above). The resulting emulsion was applied so that the drylayer was 1.0 μm thick (silver quantity: 0.5 g/m²).

The 13th layer: The second protective layer

1 kg of the emulsion used for the 3rd layer was mixed with 1 kg of 10%gelatin. The resulting emulsion was applied so that the dry layerthereof was 2 μm thick.

The 14th layer: The first protective layer

A 10% gelatin aqueous solution containing an emulsion of fine grains(grain size: 0.15 μm, 1 mol % silver iodobromide) which is notchemically sensitized was applied so that the dry layer thereof was 1 μmthick (silver quantity: 0.3 g/m²).

On the other hand, polymer coupler latexes (a), (b), (c), (d), and (e)were prepared from polymer coupler (A) (for comparison), and polymercouplers (II), (I), (III), and (X) of this invention, respectively, inthe following way. Each polymer coupler (20 g in the case of polymercoupler (A) for comparison, and an equimolar amount to the 20 g ofpolymer coupler (A) in the case of polymer couplers of this invention interms of color forming unit moiety) was dissolved with heating in 60 mlof ethyl acetate, and the resulting solution was added to 300 ml ofaqueous solution containing 15 g of gelatin and 1.2 g of sodiumlaurylsulfate, followed by dispersion by a colloid mill. Finally, theethyl acetate was removed under reduced pressure.

Using these latex dispersions in place of the magenta coupler emulsionin sample A, samples B, C, D, E, and F were prepared, respectively, inthe same way as for sample A. Each latex was used in an equimolar amountof the magenta coupler in terms of coupler unit.

The samples A to F were exposed to light and underwent the reversalcolor process. In the first experiment, the first development wasperformed for 6 minutes for standard processing; and in the secondexperiment, the first development was performed for 10 minutes forsensitization processing.

    ______________________________________                                         Processing (Standard processing)                                             ______________________________________                                        Step                Time    Temperature                                       First development   6 min   38° C.                                     Water washing       2 min   38° C.                                     Reversal            2 min   38° C.                                     Color forming development                                                                         6 min   38° C.                                     Adjustment          2 min   38° C.                                     Bleaching           6 min   38° C.                                     Fixing              4 min   38° C.                                     Water washing       4 min   38° C.                                     Stabilization       1 min   Normal temp.                                      Drying                      45° C.                                     First development                                                             Water                    700    ml                                            Sodium tetrapolyphosphate                                                                              2      g                                             Sodium sulfite           20     g                                             Hydroquinone monosulfonate                                                                             30     g                                             Sodium carbonate (monohydrate)                                                                         30     g                                             1-Phenyl-4-methyl-4-methoxy-3-                                                                         2      g                                             pyrazolidone                                                                  Potassium bromide        2.5    g                                             Potassium thiocyanate    1.2    g                                             Potassium iodode (0.1% solution)                                                                       2      ml                                            Water to make            1000   ml                                            Reversal                                                                      Water                    700    ml                                            Nitrilo-N,N,N--trimethylenesulfonic                                                                    3      g                                             acid hexasodium salt                                                          Stannous chloride (dihydrate)                                                                          1      g                                             p-Aminophenol            0.1    g                                             Sodium hydroxide         8      g                                             Glacial acetic acid      15     ml                                            Water to make            1000   ml                                            Color forming development                                                     Water                    700    ml                                            Sodium tetrapolyphosphate                                                                              2      g                                             Sodium sulfite           7      g                                             Sodium tertiary phosphate (dihydrate)                                                                  36     g                                             Potassium bromide        1      g                                             Potassium iodode (0.1% solution)                                                                       90     ml                                            Sodium hydroxide         3      g                                             Citrazinic acid          1.5    g                                             4-Amino-3-methyl-N--ethyl-                                                                             11     g                                             β-hydroxyethylaniline sesqui-                                            sulfate monohydrate                                                           Ethylenediamine          3      g                                             Water to make            1000   ml                                            Adjustment                                                                    Water                    700    ml                                            Sodium sulfite           12     g                                             Sodium ethylenediaminetetra-                                                                           8      g                                             acetate (dihydrate)                                                           Thioglycerine            0.4    ml                                            Glacial acetic acid      3      ml                                            Water to make            1000   ml                                            Bleaching                                                                     Water                    800    ml                                            Sodium ethylenediaminetetra-                                                                           2.0    g                                             acetate (dihydrate)                                                           Ferric ammonium ethylenediamine-                                                                       120.0  g                                             tetraacetic (dihydrate)                                                       Potassium bromide        100.0  g                                             Water to make            1000   ml                                            Fixing                                                                        Water                    800    ml                                            Ammonium thiosulfate     80.0   g                                             Sodium sulfite           5.0    g                                             Sodium bisulfite         5.0    g                                             Water to make            1000   ml                                            Stabilization                                                                 Water                    800    ml                                            Formalin (37 wt %)       5.0    ml                                            Fuji Dri-Wel             5.0    ml                                            Water to make            1000   ml                                            ______________________________________                                    

After development, the sensitivity of the magenta image was measured,and the difference (ΔS) between the sensitivity (*1) in sensitizationprocessing and the sensitivity in standard processing was obtained. Theresults are shown in the following Table 2.

                  TABLE 2                                                         ______________________________________                                                              Number average                                                                             Δ S                                  Sample                                                                              Coupler         molecular weight                                                                           (in log)                                   ______________________________________                                        A     Low molecular weight                                                                          --           +0.37                                            coupler                                                                 B     Polymer coupler (A)                                                                           15,000       +0.38                                            for comparison                                                          C     Polymer coupler (II)                                                                          48,000       +0.47                                      D     Polymer coupler (I)                                                                           105,000      +0.55                                      E     Polymer coupler (III)                                                                         96,000       +0.51                                      F     Polymer coupler (X)                                                                           92,000       +0.55                                      ______________________________________                                         *1: Exposure that gives a density of 1.0.                                

It is noted from this table that a polymer coupler having a high averagemolecular weight provides increased sensitization when thelight-sensitive material containing it undergoes sensitizationprocessing. Thus the light-sensitive material containing such coupler issuitable for sensitization treatment.

EXAMPLE 2

Sample (1) of multilayered color light-sensitive material was preparedby forming the following layers on a polyethylene terephthalate filmsupport.

The 1st layer: Antihalation layer

A gelatin layer containing black colloidal silver.

The 2nd layer: Interlayer

A gelatin layer containing an emulsion of 2,5-di-t-octylhydroquinone.

The 3rd layer: Slow-sensitive red sensitive emulsion layer

Silver iodobromide emulsion

(silver iodide: 5 mol %): Silver quantity: 1.6 g/m²

Sensitizing dye I

4.5×10⁻⁴ mol per mol of silver

Sensitizing dye II

1.5×10⁻⁴ mol per mol of silver

Coupler EX-1

0.04 mol per mol of silver

Coupler EX-3

0.003 mol per mol of silver

Coupler EX-9

0.0006 mol per mol of silver

The 4th layer: High-speed red sensitive emulsion layer

Silver iodobromide emulsion

(silver iodide: 10 mol %): Silver quantity: 1.4 g/m²

Sensitizing dye I

3×10⁻⁴ mol per mol of silver

Sensitizing dye II

1×10⁻⁴ mol per mol of silver

Coupler EX-1

0.002 mol per mol of silver

Coupler EX-2

0.02 mol per mol of silver

Coupler EX-3

0.0016 mol per mol of silver

The 5th layer: Interlayer

Same as the 2nd layer.

The 6th layer: Slow-speed green sensitive emulsion layer

Silver iodobromide emulsion

(silver iodide: 4 mol %): Silver quantity: 1.2 g/m²

Sensitizing dye III

5×10⁻⁴ mol per mol of silver

Sensitizing dye IV

2×10⁻⁴ mol per mol of silver

Coupler EX-4

0.05 mol per mol of silver

Coupler EX-5

0.008 mol per mol of silver

Coupler EX-9

0.0015 mol per mol of silver

The 7th layer: High-speed green sensitive emulsion layer

Silver iodobromide emulsion

(silver iodide: 8 mol %): Silver quantity: 1.3 g/m²

Sensitizing dye III

3×10⁻⁴ mol per mol of silver

Sensitizing dye IV

1.2×10⁻⁴ mol per mol of silver

Coupler EX-7

0.017 mol per mol of silver

Coupler EX-6

0.003 mol per mol of silver

Coupler EX-10

0.0003 mol per mol of silver

The 8th layer: Yellow filter layer

A gelatin layer of an emulsion containing yellow colloidal silver and2,5-di-t-octylhydroquinone in an aqueous solution of gelatin.

The 9th layer: Slow-speed blue sensitive emulsion layer

Silver iodobromide emulsion

(silver iodide: 6 mol %): Silver quantity: 0.7 g/m²

Coupler EX-8

0.25 mol per mol of silver

Coupler EX-9

0.015 mol per mol of silver

The 10th layer: High-speed blue sensitive emulsion layer Silveriodobromide emulsion

(silver iodide: 6 mol %): Silver quantity: 0.6 g/m²

Coupler EX-8

0.06 mol per mol of silver

The 11th layer: The first protective layer

A gelatin layer of an emulsion containing silver iodobromide (silveriodide: 1 mol %, average grain size: 0.07 μm, silver quantity: 0.5 g/m²)and ultravilot absorber UV-1.

The 12th layer: The second protective layer

A gelatin layer containing polymethyl methacrylate grains (about 1.5 μmin diameter).

In addition to the above-mentioned compounds, gelatin hardener H-1 andsurface active agent were added to each layer.

On the other hand, polymer coupler latexes (a), (b), (c), (d), and (e)were prepared from polymer couple (A) (for comparison), and polymercouplers (II), (I), (III), and (X) of this invention, respectively, inthe following way. Each polymer coupler (20 g in the case of polymercoupler (A) for comparison, and an equimolar amount to the 20 g ofpolymer coupler (A) in the case of polymer coupler of this invention interms of color forming unit moiety) was dissolved with heating in 60 mlof ethyl acetate, and the resulting solution was added to 300 ml ofaqueous solution containing 15 g of gelatin and 1.2 g of sodiumlaurylsulfate, followed by dispersion by a colloid mill. Finally, theethyl acetate was removed under reduced pressure.

Using these latex dispersions in place of the emulsion of magentacoupler EX-4 in sample (1), samples (2), (3), (4), (5), and (6) wereprepared, respectively, in an analogous manner as for sample (1). Eachlatex was used in an equimolar amount of the magenta coupler of sample(1) in terms of coupler unit.

The samples (1) to (6) were exposed to light and underwent the colornegative process. In the first experiment, the color development wasperformed for 3 minutes and 15 seconds for standard processing; and inthe second experiment, the color development was performed for 6 minutesand 20 seconds for sensitization processing.

The development was performed as follows at 38° C.

    ______________________________________                                        1.      Color development                                                                           3 min 15 sec                                            2.      Bleaching     6 min 30 sec                                            3.      Water washing 3 min 15 sec                                            4.      Fixing        6 min 30 sec                                            5.      Water washing 3 min 15 sec                                            6.      Stabilization 3 min 15 sec                                            ______________________________________                                    

The composition of the processing solution used for

    ______________________________________                                        Color developer                                                               Sodium nitrilotriacetate 1.0    g                                             Sodium sulfite           4.0    g                                             Sodium carbonate         30.0   g                                             Potassium bromide        1.4    g                                             Hydroxylamine sulfate    2.4    g                                             4-(N--ethyl-N--β-hydroxyethylamino)-                                                              4.5    g                                             2-methylaniline sulfate                                                       Water to make            1      liter                                         Bleaching solution                                                            Ammonium bromide         160.0  g                                             Ammonia water (28%)      25.0   cc                                            Sodium iron ethylenediamine-                                                                           130.0  g                                             tetraacetate                                                                  Glacial acetic acid      14.0   cc                                            Water to make            1      liter                                         Fixer                                                                         Sodium tetrapolyphosphate                                                                              2.0    g                                             Sodium sulfite           4.0    g                                             Ammonium thiosulfate (70%)                                                                             175.0  cc                                            Sodium bisulfite         4.6    g                                             Water to make            1      liter                                         Stabilizer                                                                    Formalin                 8.0    cc                                            Water to make            1      liter                                         ______________________________________                                    

The coupler couplers, gelatin hardener, ultraviolet absorber, andsensitizing dyes used are as follows. ##STR5##

After development, the sensitivity of the magenta image was measured,and the difference (ΔS) between the sensitivity (*1) in sensitizationprocessing and the sensitivity in standard processing was obtained. Theresults are shown in the following Table 3.

                  TABLE 3                                                         ______________________________________                                                                 Number                                                                        average                                                                       molecular ΔS                                   Sample   Coupler         weight    (in log)                                   ______________________________________                                        (1)      Polymer coupler EX-4                                                                           4,000    +0.08                                               for comparison                                                       (2)      Polymer coupler (A)                                                                           15,000    +0.09                                               for comparison                                                       (3)      Polymer coupler (II)                                                                          48,000    +0.17                                      (4)      Polymer coupler (I)                                                                           105,000   +0.17                                      (5)      Polymer coupler (III)                                                                         96,000    +0.13                                      (6)      Polymer coupler (X)                                                                           92,000    +0.16                                      ______________________________________                                         *1: Exposure that gives So. 2: Dmin + 0.2.                               

It is noted from the results set forth Table 3 that a polymer couplerhaving a high average molecular weight provides increased sensitizationwhen the light-sensitive material containing it undergoes sensitizationprocessing. Thus the light-sensitive material containing such coupler issuitable for sensitization treatment.

EXAMPLE 3

Preparation of Polymer Coupler (B) for Comparison

Polymer Coupler Latex (I) described in Synthesis Example 7 of U.S. Pat.No. 4,474,870, which has the following repeating unit: ##STR6## whereinx/y is 53.2/46.8 by weight, was replicated from monomeric coupler (a)represented by the following formula: ##STR7##

The resulting polymer is hereinafter referred to as "polymer coupler(B)". GPC gave a number average molecular weight of 12,500.

Preparation of Polymer Coupler (XI) of the Invention

A mixture of 20 g of monomeric coupler (a), 20 g of methyl acrylate, and60 g of dimethylacetamide was heated at 60° C. in a nitrogen stream.Then 5 g of dimethylacetamide containing 0.3 g of dimethylazobisisobutyrate was added to initiate polymerization. After reactionfor 5 hours, the reaction liquid was cooled and poured into 3 liters ofwater. The solid which had separated out was filtered off, washedthoroughly with water, and dried with heating under reduced pressure.Thus there was obtained 38.1 g of polymer coupler (B).

It was indicated by chlorine analysis that this polymer contains 52.8%of monomeric coupler (a). GPC gave a number average molecular weight of112,000.

Test samples were prepared in the same manner as in Example 1. Afterdevelopment, the sensitivity of the magenta image was measured, and thedifference (ΔS) between the sensitivity (*1) in sensitization processingand the sensitivity in standard processing was obtained. The results areshown in the following Table 4.

                  TABLE 4                                                         ______________________________________                                                         Number average                                                                             ΔS                                        Coupler          molecular weight                                                                           (in log)                                        ______________________________________                                        Polymer coupler (B)                                                                             12,500      +0.33                                           for comparison                                                                Polymer coupler (XI)                                                                           112,000      +0.49                                           ______________________________________                                         *1: Exposure that gives a density of 1.0.                                

It is noted from this table that a polymer coupler of the presentinvention which has a higher average molecular weight than that preparedby a known method from the same monomeric coupler provides increasedsensitization when the light-sensitive material containing it undergoessensitization processing.

EXAMPLE 4

Using monomeric coupler (C-13), polymer couplers having apyrazolotriazole moiety were prepared.

Preparation of Polymer Coupler (XII) of the Invention

A mixture of 20 g of monomeric coupler (C-13), 20 g of butyl acrylate,and 60 g of dimethylacetamide was heated at 60° C. with stirring in anitrogen stream. Then 50 g of dimethylacetamide containing 0.3 g ofdimethyl azobisisobutyrate was added to initiate polymerization. Afterreaction for 5 hours, the reaction liquid was cooled and poured into 3liters of water. The solid which had separated out was filtered off,washed thoroughly with water, and dried with heating under reducedpressure. Thus there was obtained 38.6 g of polymer coupler (XII).

It was indicated by chlorine analysis that this polymer contains 50.2%of monomeric coupler (C-13). GPC gave a number average molecular weightof 128,000.

Preparation of Polymer Coupler (C) for Comparison

A mixture of 20 g of monomeric coupler (C-13), 20 g of butyl acrylate,and 100 g of dimethylacetamide was heated at 85° C. with stirring in anitrogen stream. Then 5 g of dimethylacetamide containing 0.6 g ofdimethyl azobisisobutyrate was added to initiate polymerization. Afterreaction for 5 hours, the reaction liquid was cooled and poured into 3liters of water. The solid which had separated out was filtered off,washed thoroughly with water, and dried with heating under reducedpressure. Thus there was obtained 38.9 g of polymer coupler (C) forcomparison.

It was indicated by chlorine analysis that this copolymer contains 50.8%of monomeric coupler (C-13). GPC gave a number average molecular weightof 10,600.

Test samples were prepared in the same manner as in Example 1. Afterdevelopment, the sensitivity of the magenta image was measured, and thedifference (ΔS) between the sensitivity (*1) in sensitization processingand the sensitivity in standard processing was obtained. The results areshown in the following Table 5.

                  TABLE 5                                                         ______________________________________                                                         Number average                                                                             ΔS                                        Coupler          molecular weight                                                                           (in log)                                        ______________________________________                                        Polymer coupler (XII)                                                                          128,000      +0.30                                           Polymer coupler (C)                                                                             10,600      +0.48                                           for comparison                                                                ______________________________________                                         *1: Exposure that gives a density of 1.0.                                

It is noted from this table that a polymer coupler having a high averagemolecular weight provides increased sensitization when thelight-sensitive material containing it undergoes sensitizationprocessing.

While the invention has been described in detail and with reference tospecific embodiment thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide color light-sensitive materialcontaining a polymer coupler having an average molecular weight higherthan 30,000 and having a polymeric unit derived from a monomeric magentacoupler represented by formula (I): ##STR8## wherein R₁ is hydrogen,chlorine, or a lower alkyl group having 1 to 4 carbon atoms; A is aphenylene group, a --CONH-- group or a --COO-- group; B is anunsubstituted or substituted alkylene group, an unsubstituted orsubstituted aralkylene group, or an unsubstituted or substitutedphenylene group; Y is --O--, --NH--, --S--, --SO₂ --, --SO--, --CONH--,--COO--, --NHCO--, or --NHCONH--; Q is a residue of a magentacolor-forming coupler which forms a dye through coupling with theoxidation product of an aromatic primary amine developer; and m is 1when n is 1, and m is 0 or 1 when n is
 0. 2. A silver halide colorlight-sensitive material as in claim 1, wherein the average molecularweight of the polymer coupler is higher than 45,000.
 3. A silver halidecolor light-sensitive material as in claim 1, wherein the averagemolecular weight of the polymer coupler is higher than 80,000.
 4. Asilver halide color light-sensitive material as in claim 1, wherein thepolymer coupler is used in an amount of from 2×10⁻³ mol to 5×10⁻¹ mol,as a color-forming unit, per mol of silver.
 5. A silver halide colorlight-sensitive material as in claim 2, wherein the polymer coupler isused in an amount of from 2×10⁻³ mol to 5×10⁻¹ mol, as a color-formingunit, per mol of silver.
 6. A silver halide color light-sensitivematerial as in claim 3, wherein the polymer coupler is used in an amountof from 2×10⁻³ mol to 5×10⁻¹, as a color-forming unit, per mol ofsilver.
 7. A silver halide color light-sensitive material as in claim 4,wherein the polymer coupler is used in an amount of more than 1×10⁻²mol, as a color-forming unit, per mol of silver.
 8. A silver halidecolor light-sensitive material as in claim 5, wherein the polymercoupler is used in an amount of more than 1×10⁻² mol, as a color-formingunit, per mol of silver.
 9. A silver halide color light-sensitivematerial as in claim 6, wherein the polymer coupler is used in an amountof more than 1×10⁻² mol, as a color-forming unit, per mol of silver. 10.A silver halide color light-sensitive material as in claim 1, wherein Bis an unsubstituted or substituted alkylene group having 1 to 10 carbonatoms, an unsubstituted or substituted aralkylene group, or anunsubstituted or substituted phenylene group.
 11. A silver halide colorlight-sensitive material as in claim 2, wherein B is an unsubstituted orsubstituted alkylene group having 1 to 10 carbon atoms, an unsubstitutedor substituted aralkylene group, or an unsubstituted or substitutedphenylene group.
 12. A silver halide color light-sensitive material asin claim 3, wherein B is an unsubstituted or substituted alkylene grouphaving 1 to 10 carbon atoms, an unsubstituted or substituted aralkylenegroup, or an unsubstituted or substituted phenylene group.
 13. A silverhalide color light-sensitive material as in claim 1, wherein the residueQ of the magenta color-forming coupler is pyrazolone pyrazolotriazole orimadiazopyrazol.
 14. A silver halide color light-sensitive material asin claim 2, wherein the residue Q of the magenta color-forming formingcoupler is pyrazolone pyrazolotriazole or imadiazopyrazole.
 15. A silverhalide color light-sensitive material as in claim 3, wherein the residueQ of the magenta color-forming coupler is pyrazolone pyrazolotriazole orimadiazopyrazole.
 16. A silver halide color light-sensitive material asin claim 4, wherein the residue Q of the magenta color-forming coupleris pyrazolone pyrazolotriazole or imadiazopyrazole.
 17. A silver halidecolor light-sensitive material as in claim 7, wherein the residue Q ofthe magenta color-forming coupler is pyrazolone pyrazolotriazole orimadiazopyrazole.
 18. A silver halide color light-sensitive material asin claim 1, wherein the residue Q of the magenta color-forming coupleris 1-(2,4,6-trichlorophenyl)-2pyrazolin-5-one.
 19. A silver halide colorlight-sensitive material as in claim 1, wherein the residue Q of themagenta color-forming coupler is pyrazolo[1,5-b][1,2,4]triazole.